JP2005225981A - Film for forming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film for forming with combined heat resistance, chemical resistance, flame-retardancy, impact resistance and wet heat resistance, and especially excellent in tensile elongation and numbers of flexing by an MIT flexural test. <P>SOLUTION: This film for forming comprises a polyphenylene sulfide resin being non-oriented, having tensile elongation at 25°C of ≥20% and <100% after heat-treated at 100-280°C, impact strength of ≥0.2 N/μm and <1 N/μm, and numbers of flexing by the MIT flexural test of ≥300 and <1,000. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a molding film. More particularly, the present invention relates to a molding film particularly suitable for an electric insulation material for a car air conditioner motor or a water heater that is suitably used for a hybrid car that is currently being developed by an automobile manufacturer, and particularly excellent in workability. Is.

  Conventionally, polyphenylene sulfide (PPS) films have excellent properties such as heat resistance, flame retardancy, rigidity, chemical resistance, electrical insulation and low hygroscopicity. Electrical and electronic equipment, mechanical parts and automobiles Used for parts.

  In recent years, application of PPS films to electrical insulating materials has been promoted taking advantage of the high electrical insulation and low hygroscopicity. For example, it has been conventionally known that (1) a biaxially oriented polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) film is used as an electrical insulating material (see Patent Document 1), and (2) non-oriented. Some PPS sheets are also known (see Patent Document 2 and Patent Document 3). Further, (3) a laminate in which a biaxially oriented PPS layer is laminated on a non-oriented PPS layer without using an adhesive is known (see Patent Document 4).

However, the above conventional films and sheets, laminated films and laminates have the following problems. That is, the film (1) has poor impact resistance and tear strength. For example, when used as a slot liner or wedge for a motor, the film may be torn or the film may be delaminated. was there. In addition, the non-oriented sheet (2) has a high tear strength but a low tensile elongation, and when exposed to a temperature near the melting point, the strength rapidly decreases, and the form retainability is remarkably high. There was a problem of getting worse. Furthermore, although the laminate of (3) has high impact resistance without using an adhesive, the tensile elongation is small and there is a problem in workability.
JP 55-35456 A JP-A-56-34426 JP 57-121052 A JP-A-2-45144

  An object of the present invention is to solve these problems and to provide a molding film having heat resistance, chemical resistance, flame retardancy, impact resistance and heat and humidity resistance, and having a high tensile elongation. It is.

  The forming film of the present invention mainly has the following configuration in order to solve the above problems. That is, the molding film of the present invention is made of a non-oriented polyphenylene sulfide alloy resin, and the tensile elongation after heat treatment at a temperature of 100 ° C. or more and 280 ° C. or less is 20% or more and less than 100% at 25 ° C. It is the sheet | seat for shaping | molding characterized.

  According to a preferred aspect of the present invention, the polyphenylene sulfide alloy resin is formed by blending 5 to 15 parts by weight of an olefin copolymer with respect to 100 parts by weight of the polyphenylene sulfide resin, An epoxy group-containing olefin copolymer obtained by copolymerizing an α-olefin, an α, β-unsaturated carboxylic acid alkyl ester and an epoxy group-containing vinyl monomer is contained as an essential component.

  Further, according to a preferred aspect of the present invention, in the epoxy group-containing olefin copolymer, the proportion of α-olefin is 52 to 95 wt% in the total of α-olefin and α, β-unsaturated carboxylic acid alkyl ester. % Of α, β-unsaturated carboxylic acid alkyl ester is 5 to 48% by weight, and the total proportion of α-olefin and α, β-unsaturated carboxylic acid alkyl ester is 85 to 99.5% by weight. %, An epoxy group-containing olefin copolymer having an epoxy group-containing vinyl monomer ratio of 0.5 to 15% by weight is used.

  According to a preferred aspect of the present invention, the impact strength of the molding film is 0.2 N / μm or more and less than 1 N / μm, and the number of MIT flex tests is 300 or more and less than 1000.

  According to the present invention, as described below, it is possible to obtain a molding film having heat resistance, chemical resistance, flame retardancy, impact resistance and wet heat resistance, and having a high tensile elongation.

  In addition, the molding film made of the non-oriented polyphenylene sulfide alloy resin of the present invention is excellent in heat resistance, moist heat resistance, flame retardancy and the like, and is particularly useful as an electrical insulating material. Further, the tensile elongation and MIT The number of bending tests is large and the workability is excellent.

  Hereinafter, the best embodiment of the film for molding of the present invention will be described by way of example.

  In the present invention, the polyphenylene sulfide alloy resin refers to a resin obtained by blending an olefin copolymer with polyphenylene sulfide. The alloy here refers to a technique of blending different kinds of polymers, and is used in a different meaning from copolymerization.

  As the olefin copolymer used in the present invention, an epoxy group-containing olefin copolymer obtained by copolymerizing an α-olefin, an α, β-unsaturated carboxylic acid alkyl ester and an epoxy group-containing vinyl monomer is particularly preferable. Used.

  Further, as a particularly preferred olefin copolymer, the copolymerization ratio is α, when the proportion of α-olefin is 52 to 95% by weight in the total of α-olefin and α, β-unsaturated carboxylic acid alkyl ester. The proportion of β-unsaturated carboxylic acid alkyl ester is 5 to 48% by weight, and in the epoxy group-containing olefin copolymer, the total proportion of α-olefin and α, β-unsaturated carboxylic acid alkyl ester is An epoxy group-containing olefin copolymer having an epoxy group-containing vinyl monomer ratio of 0.5 to 15% by weight is 85 to 99.5% by weight. More preferably, the copolymerization ratio of the α-olefin and the α, β-unsaturated carboxylic acid alkyl ester is 60 to 85% by weight of the α-olefin and the α, β-unsaturated carboxylic acid alkyl ester. In the epoxy group-containing olefin copolymer, the total proportion of the α-olefin and the α, β-unsaturated carboxylic acid alkyl ester is 85 to 99.5 wt%. An epoxy group-containing olefin copolymer in which the ratio of the epoxy group-containing vinyl monomer is 0.5 to 15% by weight is exemplified.

  Specific examples of the α-olefin, which is a monomer component of such a particularly preferable epoxy group-containing olefin copolymer, include, for example, ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, decene- 1 and octene-1, among others, ethylene is preferably used. Moreover, these can also use 2 or more types simultaneously.

  In addition, the other monomer component of the particularly preferred epoxy group-containing olefin copolymer, α, β-unsaturated carboxylic acid alkyl ester, for example, an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, Alkyl esters such as acrylic acid and methacrylic acid, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, acrylic acid Examples include isobutyl, hexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate and hexyl methacrylate. Of these, methyl acrylate, methacrylate Methyl, ethyl acrylate, ethyl methacrylate, butyl n- acrylate n- butyl and methacrylic acid are preferably used. Moreover, these can also use 2 or more types simultaneously.

  In addition, as an epoxy group-containing vinyl monomer, which is another monomer component of a particularly suitable epoxy group-containing olefin copolymer, for example, glycidyl ester or glycidyl ether of α, β-unsaturated acid is exemplified. In particular, a glycidyl ester of an α, β-unsaturated acid composed of a structural unit represented by the following general formula is preferably used.

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
Specific examples of the glycidyl ester of α, β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate, and glycidyl methacrylate is particularly preferably used.

  In the present invention, polyphenylene sulfide (PPS) means 70 mol% or more (preferably 85 mol or more) of the repeating unit represented by the following structural formula.

  If the repeating unit component is less than 70 mol%, the crystallinity of the polymer (polymer), the thermal transition temperature, etc. will be low, and the heat resistance and dimensional stability characteristic of a film comprising a resin composition containing PPS as the main component will be obtained. And mechanical properties may be impaired. As long as it is less than 30 mol%, preferably less than 15 mol% of the repeating unit, a unit containing a copolymerizable sulfide bond may be contained. The copolymerization method of the polymer may be random type or block type.

  The melt viscosity of the PPS used in the present invention is not particularly limited as long as it can be melt kneaded, but usually one having a range of 100 to 1,000 poise (temperature 310 ° C., shear rate 1,000 / sec) is used. The range of 100 to 5000 poise is more preferably used.

  As described above, the polyphenylene sulfide alloy resin used in the present invention is obtained by blending an olefin copolymer with polyphenylene sulfide. The blending ratio of the olefin copolymer is 100 parts by weight of polyphenylene sulfide. The amount is preferably 5 to 15 parts by weight, more preferably 10 to 15 parts by weight. When the blending ratio of the olefin copolymer is less than 5 parts by weight, the molding film becomes brittle, and when it exceeds 15 parts by weight, the heat resistance, which is a characteristic of PPS, is lowered.

  The method for preparing the polyphenylene sulfide alloy resin used in the present invention is not particularly limited, but the mixture of raw materials is fed to a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll. As a representative example, a method of kneading at a temperature of 280 to 380 ° C. can be given. There are no particular restrictions on the mixing order of the raw materials, and all the raw materials are blended and then melt-kneaded by the above method. Some raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended and melt-kneaded. Any method may be used, such as a method, or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or biaxial extrusion method.

  The melt viscosity of the polyphenylene sulfide alloy resin used in the present invention was measured according to JIS-Z-8803 at a temperature of 310 ° C. and a shear rate of 1000 / sec using a flow tester CFT-500 manufactured by Shimadzu Corporation. The unit is expressed in poise.

  The melt viscosity of the polyphenylene sulfide alloy resin used in the present invention is not particularly limited as long as it can be melt kneaded, but usually 100 to 10000 poise (temperature 310 ° C., shear rate 1000 / sec) is used. Those in the range of 5000 poise are more preferably used.

   In the present invention, inert particles may be added in order to further improve the handleability and processability of the molding film. Examples of the inert particles herein include silica, alumina, calcium carbonate, badium carbonate, barium titanate, barium sulfate, calcium silicate, magnesium oxide, titanium oxide, and zinc oxide, and melting at 300 ° C. And particles of an organic polymer compound (for example, cross-linked polystyrene, etc.) that are not used.

  The molding film of the present invention refers to a film in which the above polyphenylene sulfide alloy resin is melted and formed into a sheet shape. The method of forming the polyphenylene sulfide alloy resin into a sheet is not particularly limited, but from the viewpoint of thickness unevenness and die streaks, it is applied by applying static electricity to adhere to the cooling drum to form a sheet, or it is extruded by a calendar roll. A method of calendering and winding the polyphenylene sulfide alloy resin is preferable.

  For example, the polyphenylene sulfide alloy resin is supplied to a uniaxial or biaxial small extruder, melt-kneaded, and then discharged from the die into a sheet. A method is preferred in which the discharged molten sheet is brought into close contact with a chromium plating roll at 5 ° C. to 90 ° C. by an electrostatic application cast method at an applied voltage of 4 to 10 kV, and is cooled and solidified to obtain a sheet-like film.

  In the molding film of the present invention, the tensile elongation after heat treatment at a temperature of 100 ° C. or more and 280 ° C. or less is less than 100% and 20% or more at 25 ° C., more preferably less than 50% and 20%. That's it. In order to make the tensile elongation within the above range, the cooling drum temperature at the time of melt molding is important. Specifically, by setting the cooling drum temperature in the range of 5 ° C. to 90 ° C., the tensile elongation can be made less than 100% and 20% or more, and the cooling drum temperature is set in the range of 60 ° C. to 90 ° C. By setting, the tensile elongation can be less than 50% and 20% or more.

  The impact strength of the molding film of the present invention is preferably 0.2 N / μm or more and less than 1 N / μm from the viewpoint of durability. The number of MIT flex tests of the molding film of the present invention is preferably 300 times or more and less than 1000 times from the viewpoint of durability. Here, durability refers to a change over time due to an external force when continuously used in an electrically insulating material such as a motor.

  In order to make the impact strength and the number of MIT flexes within the above ranges, the cooling drum temperature at the time of melt molding is important. Specifically, by setting the cooling drum temperature in the range of 5 ° C. to 90 ° C., the impact strength can be 0.2 N / μm or more and less than 1 N / μm, and the MIT flex number is 300 times or more, 1000 Less than once.

  At least one surface of the molding film of the present invention can be subjected to corona discharge treatment or plasma treatment as necessary. Moreover, the thickness of the whole film for molding of the present invention is preferably in the range of 20 to 700 μm from the thickness range of the film used for the electrically insulating material.

  The molding film made of the non-oriented polyphenylene sulfide alloy resin of the present invention is excellent in heat resistance, moist heat resistance and flame retardancy, and is particularly useful as an electrical insulating material. Also, tensile elongation and MIT flex test It is a material with a large number of times and excellent workability.

[Measurement method of characteristics]
(A) Tensile elongation of forming film A sample that had been heat-treated for 30 minutes in an atmosphere at 150 ° C. and 180 ° C. was measured using “Tensilon” (AMF / RTA-100 manufactured by Orientec Co., Ltd.). A 10 mm sample film is set so that the length between chucks is 50 mm, and a tensile test is performed at 25 ° C. and 65% RH at a tensile speed of 300 mm / min.
(B) Impact strength of molding film The Charpy impact test is measured according to ASTM D256.
(C) MIT flex test of molding film MIT flex test is measured according to JIS-P-8115 method.

(Examples 1 to 24)
A method for preparing the PPS alloy resin used in the examples of the present invention is shown below.
(A) PPS resin:
Linear PPS resin, melt viscosity 500 poise (310 ° C., shear rate 1000 / sec),
Ash content 0.05% by weight
(B) Epoxy group-containing olefin copolymer:
b1: Ethylene / methyl acrylate / glycidyl methacrylate
= 64/30/6 (wt%) copolymer.

b2: Ethylene / n-butyl acrylate / glycidyl methacrylate
= 79/15/6 (wt%) copolymer.

b3: Ethylene / methyl acrylate / glycidyl methacrylate
= 38.7 / 59 / 2.3 (wt%) copolymer.

    b4: ethylene / glycidyl methacrylate = 88/12 (% by weight) copolymer.

    b5: ethylene / butene = 92/8 (% by weight) copolymer.

  After dry blending the above (a) PPS resin and the above (b) epoxy group-containing olefin copolymer at a ratio shown in Table 1, the cylinder temperature is 280 ° C. (hopper side) to 320 ° C. (tip side). The mixture was melt-kneaded with a twin-screw extruder set to 1, pelletized with a strand cutter, and dried at 120 ° C. overnight. The obtained PPS alloy resins are referred to as Resins 1 to 4 as shown in Table 1.

  Next, the preparation method of the non-oriented PPS alloy resin film used in the Example of this invention is shown below. Each PPS alloy resin pellet adjusted as shown in Table 1 is supplied to a small extruder set at a cylinder temperature of 285 ° C. (hopper side) to 300 ° C. (tip side), melt-kneaded, and then discharged from the die into a sheet. did. The discharged molten sheet was brought into close contact with the chrome plating roll by an electrostatic application casting method at an applied voltage of 7 kV, and cooled and solidified at the cooling drum temperatures shown in Tables 2 to 4 to obtain a sheet-like film. The sheet-like films thus obtained are referred to as sheets 1 to 4 as shown in Table 1. Moreover, the rotational speed of the cooling drum was changed, and each film with different thicknesses shown in Tables 2 to 4 was obtained.

  As shown in Tables 2 to 4, the sheets 1 to 4 obtained by the above method were subjected to a heat treatment for 30 minutes in an atmosphere of 150 ° C. and 180 ° C., respectively. The film thus obtained was measured for tensile elongation, impact strength, and number of MIT flex tests. The results are shown in Tables 2-4.

(Comparative Examples 1-6)
The preparation method of a non-oriented PPS resin film is shown below. After supplying the PPS resin of only the above (a) not containing an epoxy group-containing olefin copolymer to a small extruder set at a cylinder temperature of 285 ° C. (hopper side) to 300 ° C. (tip side), and melt-kneading The sheet was discharged from the base. The discharged molten sheet was brought into close contact with the chrome plating roll by an electrostatic application casting method at an applied voltage of 7 kV, and cooled and solidified at the cooling drum temperature shown in Table 5 to obtain a sheet-like film. The sheet-like film thus obtained is designated as sheet 5 as shown in Table 1. The rotation speed of the cooling drum was changed to obtain films having different thicknesses shown in Table 5.

  The sheet 5 obtained by the above method was subjected to a heat treatment for 30 minutes in each atmosphere at 150 ° C. and 180 ° C. as shown in Table 5. The film thus obtained was measured for tensile elongation, impact strength, and number of MIT flex tests. The results are shown in Table 5.

  The molding film made of the non-oriented polyphenylene sulfide alloy resin of the present invention is excellent in heat resistance, moist heat resistance and flame retardancy, and is particularly useful as an electrical insulating material. Also, tensile elongation and MIT flex test It is a material with a large number of times and excellent workability.

  Therefore, it is useful as an electrical insulating material for motors for car air conditioners and water heaters used in hybrid cars and the like that are being developed by automobile manufacturers.

Claims (5)

A molding film comprising a non-oriented polyphenylene sulfide alloy resin and having a tensile elongation after heat treatment at a temperature of 100 ° C. or more and 280 ° C. or less of 20% or more and less than 100% at 25 ° C. The polyphenylene sulfide alloy resin comprises 5 to 15 parts by weight of an olefin copolymer based on 100 parts by weight of the polyphenylene sulfide resin, and the olefin copolymer is an α-olefin, an α, β-unsaturated carboxylic acid. 2. The molding film according to claim 1, comprising an epoxy group-containing olefin copolymer obtained by copolymerizing an alkyl ester and an epoxy group-containing vinyl monomer as essential components. In the total of α-olefin and α, β-unsaturated carboxylic acid alkyl ester in the epoxy group-containing olefin copolymer, the proportion of α-olefin is 52 to 95% by weight, and α, β-unsaturated carboxylic acid alkyl ester The proportion of the total of the α-olefin and the α, β-unsaturated carboxylic acid alkyl ester is 85 to 99.5% by weight, and the proportion of the epoxy group-containing vinyl monomer is 0.00. The film for molding according to claim 2, wherein the film is 5 to 15% by weight. Impact strength is 0.2 N / micrometer or more and less than 1 N / micrometer, The film for shaping | molding in any one of Claims 1-3 characterized by the above-mentioned. The molding film according to claim 1, wherein the number of MIT flex tests is 300 times or more and less than 1000 times.